EP0867428A1 - Method for preparing diaryl carbonates employing beta-diketone salts - Google Patents
Method for preparing diaryl carbonates employing beta-diketone salts Download PDFInfo
- Publication number
- EP0867428A1 EP0867428A1 EP98302049A EP98302049A EP0867428A1 EP 0867428 A1 EP0867428 A1 EP 0867428A1 EP 98302049 A EP98302049 A EP 98302049A EP 98302049 A EP98302049 A EP 98302049A EP 0867428 A1 EP0867428 A1 EP 0867428A1
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- EP
- European Patent Office
- Prior art keywords
- bromide
- palladium
- diketone
- salt
- cocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
Definitions
- This invention relates to the preparation of diaryl carbonates by carbonylation. More particularly, it relates to the improvement of shelf life and activity of the catalysts employed in the carbonylation reaction.
- Diaryl carbonates are valuable intermediates for the preparation of polycarbonates by transesterification with bisphenols in the melt.
- This method of polycarbonate preparation has environmental advantages over methods which employ phosgene, a toxic gas, as a reagent and environmentally detrimental chlorinated aliphatic hydrocarbons such as methylene chloride as solvents.
- diaryl carbonate is recovered as an adduct with the hydroxyaromatic compound leaving the catalyst constituents in solution in further hydroxyaromatic compound.
- such solutions have very short shelf life.
- the present invention is based on the discovery of a series of Group VIIIB metal compounds which have numerous advantages when used as catalyst constituents in carbonylation. These advantages include long shelf life under normal storage conditions even in contact with reagent and other catalyst constituents, high activity upon recycle and capability of employment at relatively low temperatures.
- the invention in one of its aspects is a method for preparing a diaryl carbonate which comprises contacting at least one hydroxyaromatic compound with oxygen and carbon monoxide in the presence of an amount effective for carbonylation of at least one catalytic material comprising a Group VIIIB metal salt of at least one aliphatic ⁇ -diketone.
- Another aspect of the invention is storage stable catalyst compositions comprising a Group VIIIB metal salt of at least one aliphatic ⁇ -diketone, an inorganic cocatalyst, an organic cocatalyst and a chloride or bromide source, said composition being in solution in at least one hydroxyaromatic compound.
- Any hydroxyaromatic compound may be employed in the present invention.
- Monohydroxyaromatic compounds such as phenol, the cresols, the xylenols and p-cumylphenol, are generally preferred with phenol being most preferred.
- the invention may, however, also be employed with dihydroxyaromatic compounds such as resorcinol, hydroquinone and 2,2-bis(4-hydroxyphenyl)propane or "bisphenol A", whereupon the products are polycarbonates.
- An essential constituent of the catalytic material employed according to the invention is a Group VIIIB metal salt of at least one aliphatic ⁇ -diketone.
- ⁇ -diketone is meant a compound containing two keto carbonyl groups separated by a single carbon atom, usually but not necessarily in the form of a CH 2 linkage.
- Suitable ⁇ -diketones include 2,4-pentanedione, 2,4-hexanedione and 3,5-heptanedione.
- the diketone salts of divalent metals are preferred, with the palladium(II) salt of 2,4-pentanedione being most preferred.
- the catalytic material preferably also includes an inorganic cocatalyst of the type disclosed in the aforementioned U.S. Patent 5,231,210 and/or an organic cocatalyst of the type disclosed in the aforementioned U.S. Patent 5,284,964. It is preferred to employ both an inorganic and an organic cocatalyst.
- Typical inorganic cocatalysts are complexes of cobalt(II) salts with organic compounds capable of forming complexes, especially pentadentate complexes, therewith.
- Illustrative organic compounds of this type are nitrogen-heterocyclic compounds including pyridines, bipyridines, terpyridines, quinolines, isoquinolines and biquinolines; aliphatic polyamines such as ethylenediamine and tetraalkylethylenediamines; crown ethers; aromatic or aliphatic amine ethers such as cryptanes; and Schiff bases.
- the especially preferred inorganic cocatalyst is a cobalt(II) complex with bis[3-(salicylalamino)propyl]methylamine, said complex hereinafter being designated "CoSMDPT".
- Suitable organic cocatalysts include various terpyridine, phenanthroline, quinoline and isoquinoline compounds including 2,2':6',2"-terpyridine, 4'-methylthio-2,2':6',2"-terpyridine and 2,2':6',2"-terpyridine N-oxide, 1,10-phenanthroline, 2,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl-1,10,phenanthroline and 3,4,7,8-tetramethyl-1,10-phenanthroline.
- the terpyridines and especially 2,2':6',2"-terpyridine are generally preferred.
- the catalytic material also preferably contains a chloride or bromide, preferably bromide, source . It may be a quaternary ammonium or phosphonium salt, as disclosed in the aforementioned patents, or a hexaalkylguanidinium chloride or bromide as disclosed in copending application No. 98300911.9.
- the guanidinium salts are often preferred; they include the a,w-bis(pentaalkylguanidinium)alkane salts. Salts in which the alkyl groups contain 2-6 carbon atoms and especially hexaethyl-guanidinium bromide are particularly preferred.
- the palladium ⁇ -diketone salt may be stored in a single vessel in solution in the hydroxyaromatic compound and in combination with the inorganic cocatalyst, the organic cocatalyst and the chloride or bromide source. If it is more convenient to store various catalyst precursor compositions in separate batches, usually no more than two, that may also be done.
- the proportion of Group VIIIB metal salt employed is an amount sufficient to provide about 1 gram-atom of metal per 800-10,000 and preferably 2,000 -5,000 moles of hydroxyaromatic compound.
- For each gram-atom of Group VIIIB metal there is usually employed about 0.1-5.0 and especially about 0.5-1.5 gram-atoms of cobalt, about 0.1-3.0 and preferably about 0.3-1.0 moles of organic cocatalyst and about 5-150, preferably about 20-50, moles of chloride or bromide source.
- Gas is supplied to the reaction mixture in proportions of about 2-50 mole percent oxygen, with the balance being carbon monoxide.
- the gases may be introduced separately or as a mixture, to a total pressure in the range of about 10-250 atmospheres.
- Reaction temperatures in the range of about 60-150°C are typical, with temperatures in the range of about 80-110° and especially about 90-100°C often being preferred by reason of decreased energy usage and the ability to employ gas proportions substantially lower in oxygen.
- Drying agents typically molecular sieves, may be present in the reaction vessel. In order for the reaction to be as rapid as possible, it is preferred to maintain the reaction pressure in accordance with the aforementioned U.S. Patent 5,399,734 until conversion of the hydroxyaromatic compound is complete.
- the diaryl carbonates produced by the method of this invention may be isolated by conventional techniques. It is often preferred to form and thermally crack an adduct of the diaryl carbonate with the hydroxyaromatic compound, as described in U.S. Patents 5,239,106 and 5,312,955.
- a phenolic solution of palladium(II) 2,4-pentanedionate (500 ppm palladium) and 2,2':6',2"-terpyridine (0.33 equivalent) was placed in a 100-ml 3-necked round-bottomed flask fitted with a magnetic stirrer, nitrogen inlet and serum cap, and having a metal alloy coupon corresponding to a typical pressure reaction vessel suspended therein to simulate reactor conditions prior to carbonylation.
- the solution was clear and orange-yellow in color. It was heated at 60°C under nitrogen, with stirring, for nine days, with samples periodically being removed for analysis. No precipitation or loss of soluble palladium was observed.
- Example 1 The procedure of Example 1 was repeated, except that the phenolic solution further contained 1 equivalent of CoSMDPT and 10 equivalents of hexaethylguanidinium bromide. No precipitation or loss of soluble palladium was observed after 21 days. By contrast, a control containing palladium(II) acetate lost 56% of its palladium by precipitation over seven days.
- a constant composition gas flow reactor system as disclosed in the aforementioned U.S. Patent 5,399,734, was charged with 60.06 g (638 mmol) of phenol, 1001 mg (3.27 mmol) of hexaethylguanidinium bromide, 124.4 mg (0.303 mmol) of CoSMDPT, 23.9 mg (0.101 mmol) of 2,2':6',2"-terpyridine and 87.4 mg (0.288 mmol) of palladium(II) 2,4-pentanedionate (500 ppm palladium).
- Molecular sieves, 37 g were placed in a perforated polytetrafluoroethylene basket mounted to the stir shaft of the reactor.
- the reactor was sealed and heated to 110°C, with stirring, and a mixture of 12.8 mole percent oxygen and 87.2 mole percent carbon monoxide was introduced at a flow rate of 344 ml/min and a pressure of about 44 atmospheres. Gas flow was continued for 2 hours, after which a portion of the reaction mixture was removed and analyzed by high pressure liquid chromatography.
- Example 3 The procedure of Example 3 was repeated, using the catalyst composition of Example 2 diluted with phenol to the concentrations of catalyst constituents recited in Example 3. The yield of diphenyl carbonate was 38.4%. Thus, it is apparent that the catalyst compositions of the invention are storage stable.
- a simulated carbonylation reaction mixture was prepared by incorporating the catalyst constituents described in Example 3 in a mixture of 42 parts of diphenyl carbonate and 58 parts of phenol, in the same proportions (i.e., 500 ppm palladium). The resulting homogeneous mixture was transferred to a stirred crystallizer maintained at 35°C. After several hours, the crystallized mixture was drained into a Buchner funnel at 35°C and the diphenyl carbonate-phenol adduct was separated by filtration and washed with a homogeneous 10:90 diphenyl carbonate-phenol mixture.
- the mother liquor was diluted with phenol to produce a mixture again containing 500 ppm of palladium, and said mixture was carbonylated as described in Example 3 except that the gas feed contained 9.1 mole percent oxygen.
- the yield of diphenyl carbonate after 2 hours was 51.5%, in comparison with 51.7% for a freshly prepared palladium(II) 2,4-pentanedionate-containing catalyst.
- Example 3 The procedure of Example 3 was repeated at various temperatures and oxygen levels, using both palladium(II) 2,4-pentanedionate and palladium(II) acetate as catalyst constituents.
- the results are given in Table II.
Abstract
Description
Pd(II) Salt | Diphenyl carbonate yield. % |
2,4-Pentanedionate, fresh | 42.9 |
2,4-Pentanedionate, stored | 35.4 |
Acetate, fresh | 43.3 |
Acetate, stored | 14.0 |
Pd(II) salt | Temp., °C | Oxygen, mole % | Diphenyl carbonate yield, % |
2,4-pentanedionate | 110 | 12.8 | 42.9 |
2,4-pentanedionate | 100 | 9.1 | 44.4 |
2,4-pentanedionate | 90 | 9.1 | 35.4 |
2,4-pentanedionate | 80 | 9.1 | 27.2 |
Acetate | 110 | 12.8 | 43.3 |
Acetate | 90 | 9.1 | 18.9 |
Claims (10)
- A method for preparing a diaryl carbonate which comprises contacting at least one hydroxyaromatic compound with oxygen and carbon monoxide in the presence of an amount effective for carbonylation of at least one catalytic material comprising a Group VIIIB metal salt of at least one aliphatic β-diketone.
- A method according to claim 1 wherein the Group VIIIB metal is palladium.
- A method according to claim 2 wherein the palladium(II) salt is palladium(II) 2,4-pentanedionate.
- A method according to claim 3 wherein the hydroxyaromatic compound is phenol.
- A method according to claim 1 wherein the catalytic material further comprises a cobalt(II) salt with an organic compound capable of forming a pentadentate complex.
- A method according to claim 1 wherein the catalytic material further comprises a terpyridine, phenanthroline, quinoline or isoquinoline compound as an organic cocatalyst.
- A method according to claim 1 wherein the catalytic material further comprises a chloride or bromide source.
- A method according to claim 7 wherein the chloride or bromide source is a quaternary ammonium bromide, quaternary phosphonium bromide or hexaalkylguanidinium bromide,
- A storage stable composition comprising a Group VIIIB metal salt of at least one aliphatic β-diketone, an inorganic cocatalyst, an organic cocatalyst and a chloride or bromide source, said composition being in solution in at least one hydroxyaromatic compound.
- A composition according to claim 9 wherein the aliphatic β-diketone is 2,4-pentanedione.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US823784 | 1992-01-22 | ||
US08/823,784 US5908952A (en) | 1997-03-24 | 1997-03-24 | Method for preparing diaryl carbonates employing β-diketone salts |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0867428A1 true EP0867428A1 (en) | 1998-09-30 |
EP0867428B1 EP0867428B1 (en) | 2004-03-03 |
Family
ID=25239705
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98302049A Expired - Lifetime EP0867428B1 (en) | 1997-03-24 | 1998-03-18 | Method for preparing diaryl carbonates employing beta-diketone salts |
Country Status (5)
Country | Link |
---|---|
US (1) | US5908952A (en) |
EP (1) | EP0867428B1 (en) |
JP (1) | JPH10330325A (en) |
DE (1) | DE69822015T2 (en) |
SG (1) | SG77629A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1024132A1 (en) * | 1998-06-01 | 2000-08-02 | General Electric Company | Method for preparing diaryl carbonates with improved selectivity |
WO2002088289A2 (en) * | 2001-04-30 | 2002-11-07 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as oxidation catalysts |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6191060B1 (en) * | 1998-12-18 | 2001-02-20 | General Electric Company | Reclamation of metal catalysts used in the production of diaryl carbonates |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0503581A2 (en) * | 1991-03-14 | 1992-09-16 | Idemitsu Kosan Company Limited | Process for producing an aromatic organic carbonate |
US5231210A (en) * | 1992-08-17 | 1993-07-27 | General Electric Company | Method for making aromatic carbonates |
EP0663388A1 (en) * | 1994-01-12 | 1995-07-19 | Mitsubishi Chemical Corporation | Method of producing aromatic carbonate |
EP0667336A1 (en) * | 1994-02-02 | 1995-08-16 | Bayer Ag | Process for the continuous preparation of diaryle carbonates |
EP0736512A1 (en) * | 1993-03-08 | 1996-10-09 | Mitsubishi Chemical Corporation | Method of producing aromatic carbonate |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4187242A (en) * | 1976-10-12 | 1980-02-05 | General Electric Company | Catalytic aromatic carbonate process |
JP2531931B2 (en) * | 1991-07-29 | 1996-09-04 | ゼネラル・エレクトリック・カンパニイ | Aromatic Organic Carbon Manufacturing Method |
US5284964A (en) * | 1992-08-17 | 1994-02-08 | General Electric Company | Method for making aromatic carbonates |
DE59404719D1 (en) * | 1993-11-22 | 1998-01-15 | Bayer Ag | Process for the preparation of diaryl carbonates |
-
1997
- 1997-03-24 US US08/823,784 patent/US5908952A/en not_active Expired - Fee Related
-
1998
- 1998-03-11 SG SG1998000550A patent/SG77629A1/en unknown
- 1998-03-16 JP JP10064848A patent/JPH10330325A/en not_active Withdrawn
- 1998-03-18 DE DE69822015T patent/DE69822015T2/en not_active Expired - Fee Related
- 1998-03-18 EP EP98302049A patent/EP0867428B1/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0503581A2 (en) * | 1991-03-14 | 1992-09-16 | Idemitsu Kosan Company Limited | Process for producing an aromatic organic carbonate |
US5231210A (en) * | 1992-08-17 | 1993-07-27 | General Electric Company | Method for making aromatic carbonates |
EP0736512A1 (en) * | 1993-03-08 | 1996-10-09 | Mitsubishi Chemical Corporation | Method of producing aromatic carbonate |
EP0663388A1 (en) * | 1994-01-12 | 1995-07-19 | Mitsubishi Chemical Corporation | Method of producing aromatic carbonate |
EP0667336A1 (en) * | 1994-02-02 | 1995-08-16 | Bayer Ag | Process for the continuous preparation of diaryle carbonates |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1024132A1 (en) * | 1998-06-01 | 2000-08-02 | General Electric Company | Method for preparing diaryl carbonates with improved selectivity |
WO2002088289A2 (en) * | 2001-04-30 | 2002-11-07 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as oxidation catalysts |
WO2002088289A3 (en) * | 2001-04-30 | 2003-02-27 | Ciba Sc Holding Ag | Use of metal complex compounds as oxidation catalysts |
US7161005B2 (en) | 2001-04-30 | 2007-01-09 | Ciba Specialty Chemicals Corporation | Use of metal complex compounds as oxidation catalysts |
US7456285B2 (en) | 2001-04-30 | 2008-11-25 | Ciba Specialty Chemicals Corp. | Use of metal complex compounds as oxidation catalysts |
US7692004B2 (en) | 2001-04-30 | 2010-04-06 | Ciba Specialty Chemicals Corporation | Use of metal complex compounds as oxidation catalysts |
US8044013B2 (en) | 2001-04-30 | 2011-10-25 | Basf Se | Use of metal complex compounds as oxidation catalysts |
Also Published As
Publication number | Publication date |
---|---|
JPH10330325A (en) | 1998-12-15 |
US5908952A (en) | 1999-06-01 |
DE69822015T2 (en) | 2005-03-03 |
SG77629A1 (en) | 2001-01-16 |
DE69822015D1 (en) | 2004-04-08 |
EP0867428B1 (en) | 2004-03-03 |
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